Wet etch chemistry for selective silicon etch

ABSTRACT

For a metal gate replacement integration scheme, the present disclosure describes removing a polysilicon gate electrode with a highly selective wet etch chemistry without damaging surrounding layers. For example, the wet etch chemistry can include one or more alkaline solvents with a steric hindrance amine structure, a buffer system that includes tetramethylammonium hydroxide (TMAH) and monoethanolamine (MEA), one or more polar solvents, and water.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional PatentApplication No. 62/434,740, titled “Wet Etch Chemistry for SelectiveSilicon Etch,” filed on Dec. 15, 2016, which is incorporated byreference herein in its entirety.

BACKGROUND

In a replacement metal gate integration scheme, wet etch chemistriesused for a polysilicon removal process can exhibit non-ideal etchselectivity between polysilicon and silicon oxide or between polysiliconand silicon nitride layers. A non-deal selectivity for the etchingchemistry could mean that the surrounding materials will be etched ordamaged during the polysilicon removal process, which can result indefects (e.g., particle generation, material diffusion, materialdegradation, etc.), electrical performance degradation (e.g., leakagecurrent), and wafer yield loss.

BRIEF DESCRIPTION OF THE DRAWINGS

Aspects of the present disclosure are best understood from the followingdetailed description when read with the accompanying figures. It isnoted that, in accordance with the common practice in the industry,various features are not drawn to scale. In fact, the dimensions of thevarious features may be arbitrarily increased or reduced for clarity ofdiscussion.

FIG. 1 shows an exemplary field effect transistor structure with asacrificial polysilicon gate electrode, according to some embodiments.

FIG. 2 shows an exemplary structure that has been subjected to apolysilicon wet etch process that exhibits poor polysilicon selectivity.

FIG. 3 shows a flow chart of an exemplary gate electrode replacementmethod that uses an exemplary wet etch chemistry to remove a sacrificialpolysilicon gate electrode, according to some embodiments.

FIG. 4 shows an exemplary gate stack that includes a gate dielectric anda gate electrode, according to some embodiments.

FIG. 5 shows an exemplary gate stack with first spacers, according tosome embodiments.

FIG. 6 shows an exemplary gate stack with first spacers and source/drainextensions, according to some embodiments.

FIG. 7 shows an exemplary gate stack with first spacers, source/drainextensions, and second spacers, according to some embodiments.

FIG. 8 shows an exemplary gate stack with first spacers, source/drainextensions, second spacers, and source/drain regions, according to someembodiments.

FIG. 9 shows an exemplary gate stack with a recessed gate electrodeafter a dry etch process, according to some embodiments.

DETAILED DESCRIPTION

The following disclosure provides different embodiments, or examples,for implementing different features of the provided subject matter.Specific examples of components and arrangements are described below tosimplify the present disclosure. These are, of course, merely examplesand are not intended to be limiting. For example, the formation of afirst feature over a second feature in the description that follows mayinclude embodiments in which the first and second features are formed indirect contact, and may also include embodiments in which additionalfeatures may be formed between the first and second features, such thatthe first and second features may not be in direct contact. In addition,the present disclosure may repeat reference numerals and/or letters inthe various examples. This repetition does not in itself dictate arelationship between the various embodiments and/or configurationsdiscussed.

Further, spatially relative terms, such as “beneath,” “below,” “lower,”“above,” “upper” and the like, may be used herein for ease ofdescription to describe one element or feature's relationship to anotherelement(s) or feature(s) as illustrated in the figures. The spatiallyrelative terms are intended to encompass different orientations of thedevice in use or operation in addition to the orientation depicted inthe figures. The apparatus may be otherwise oriented (rotated 90 degreesor at other orientations) and the spatially relative descriptors usedherein may likewise be interpreted accordingly.

The term “nominal” as used herein refers to a desired, or target, valueof a characteristic or parameter for a component or a process operation,set during the design phase of a product or a process, together with arange of values above and/or below the desired value. The range ofvalues is typically due to slight variations in manufacturing processesor tolerances. Unless defined otherwise, all technical and scientificterms used herein have the same meanings as commonly understood by oneof ordinary skill in the art to which this disclosure belongs.

Wet etch is a process that uses a chemical solution, which containsliquid etchants, to remove materials from the surface of a target suchas, for example, a wafer. A wet etch process can involve multiplechemical reactions that consume the original reactants and produce newreactants and byproducts. The wet etch process can be divided into threesteps: (1) diffusion of the liquid etchant to the “target” material; (2)the reaction between the liquid etchant and the target material; and (3)diffusion of the byproducts in the solution, away from the surface wherethe reaction occurred.

A chemical solution property in such a wet etch process is the abilityto remove the desired material without damaging, or attacking, othermaterials exposed to the wet etch chemistry. The etching system'sability to do this depends on the ratio of the etch rates between thetarget material and other material(s) present during the etchingprocess. This etch rate ratio is known as “selectivity.” Consequently, awet etch process with “high” selectivity (e.g., greater than 1000 to 1)can remove the target material without damaging any other materials thatare concurrently exposed to the wet etch chemistry. Conversely, a wetetch process with “low” selectivity (e.g., less than 1000 to 1) canremove the target material and at least part of any other material thatis exposed to the wet etch chemistry.

Wet etch processes are used in chip manufacturing at various waferfabrication stages to selectively remove materials from the wafer'ssurface. For example, wet etch can be used to remove polycrystallinesilicon (polysilicon) from a sacrificial gate structure so that it canbe replaced with a metal gate. Since the polysilicon is surrounded byother materials (e.g., silicon oxide, silicon nitride, and siliconcarbon nitride), it is important to ensure that the wet etch chemistryhas high selectivity towards polysilicon. If the selectivity is poor,the surrounding materials will be etched or damaged during thepolysilicon removal process. Poor selectivity is undesirable and canresult in defects (e.g., particle generation, material diffusion,material degradation, etc.), electrical performance degradation (e.g.,leakage current), and wafer yield loss.

The present disclosure is directed to a wet etch chemistry whichexhibits high selectivity for polysilicon and amorphous silicon (a-Si)materials and low selectivity for silicon-based oxides, nitrides, andoxycarbides. The wet etch chemistry can therefore remove polysilicon anda-Si without damaging any silicon oxide (SiO₂), silicon nitride(Si_(x)N_(y)), or silicon oxycarbide (SiO_(x)C_(y)) which are materialsthat may concurrently be exposed to the etching chemistry during the wetetch removal process. In some embodiments, this selective wet etch canbe accomplished with the use of a co-solvent system (i.e., multiplesolvents) in a semi-aqueous environment. That is, the selective wet etchchemistry can include at least two organic solvents (e.g., alkalinesolvent and/or a polar solvent) and water. In some embodiments, theorganic solvents can have a steric hindrance amine structure that caninhibit the reaction between the etching chemistry and materials such asSiO₂, Si_(x)N_(y), or SiO_(x)C_(y). In some embodiments, the wet etchchemistry can include a buffer system to ensure that the etch rateremains stable during the wet etch process. Further, small amounts ofwater or other bulk chemicals can be automatically introduced atpredetermined intervals to replenish any consumed chemicals; thereforeensuring that the solution's pH and alkali concentration are stable.

FIG. 1 is a cross-sectional view of an exemplary field effect transistor(FET) structure 100, according to some embodiments. By way of exampleand not limitation, FET structure 100 can be a finFET or a planartransistor. Exemplary structure 100 includes a semiconductor substrate110 with lightly doped regions 120 and heavily doped regions 130.Lightly doped regions 120 are known as lightly doped drain (LDD) regionsor source/drain extensions. Heavily doped regions 130 are thesource/drain regions or junctions of the FET as would be understood by aperson of ordinary skill in the art.

If exemplary structure 100 is a planar transistor, then semiconductorsubstrate 110 can be a bulk wafer or the top layer of a semiconductor oninsulator (SOI) wafer. If exemplary structure 100 is a finFET thensemiconductor substrate 110 can be a semiconductor fin, which isperpendicular to the wafer's top surface. By way of example and notlimitation, semiconductor substrate 110 can be made of silicon oranother elementary semiconductor such as, for example, germanium; acompound semiconductor including silicon carbide, gallium arsenide(GaAs), gallium phosphide (GaP), indium phosphide(InP), indium arsenide(InAs), and/or indium antimonids (InSb); an alloy semiconductorincluding silicon germanium (SiGe), gallium arsenide phosphide (GaAsP),aluminum indium arsenide (AlInAs), aluminum gallium arsenide (AlGaAs),gallium indium arsenide (GaInAs), gallium indium phosphide (GaInP),and/or gallium indium arsenide phosphide (GaInAsP); or combinationsthereof.

Exemplary FET structure 100 also includes a gate structure 140. Gatestructure 140 further includes a gate electrode 150, a gate dielectric160, and first spacers 170 and second spacers 180. Gate electrode 150and gate dielectric 160 are referred to as a “gate stack.” As would beunderstood by a person of ordinary skill in the art, gate structure 140can include a sacrificial gate electrode formed during a replacementgate process. In a replacement gate process, gate electrode 150 is asacrificial gate electrode made of polysilicon that can be replaced witha metal gate electrode in subsequent operations. By way of example andnot limitation, gate dielectric 160 is SiO₂, which can be replaced witha high dielectric constant (k value greater than 3.9) dielectric or adielectric stack, such as hafnium oxide (HfO₂), hafnium silicate(Hf-silicate), SiO₂/HfO₂, or SiO₂/Hf-silicate. In some embodiments,first spacers 170 can be a dielectric material such as, for example,SiO₂, silicon oxynitride (SiON), carbon-doped silicon nitride (SiCN),SiO_(x)C_(y), or Si_(x)N_(y). In some embodiments, the thickness offirst spacers 170 can range from about 2 nm to about 5 nm. In someembodiments, second spacers 180 can be made of a dielectric materialsuch as, for example, SiON, Si_(x)N_(y), or SiCN. As would be understoodby a person of ordinary skill in the art, second spacer 180 can be astack of one or more layers made of the same or different materials. Thefirst spacers 170 and second spacers 180 can be used to define thelightly doped regions 120 and heavily doped region 130 and to providestructural support to the gate structure during the gateelectrode/dielectric replacement process. It has to be noted that firstspacers 170 and second spacers 180 are not removed during thepolysilicon and SiO₂ removal process.

Interlayer dielectric (ILD) 190 abuts gate structure 140. In someembodiments, ILD 190 can be SiO₂, SiO_(x)C, SiON, silicon-oxy-carbonnitride (SiOCN), silicon carbide (SiC), SiCN, or a low-k material with ak value lower than 3.9. As would be understood by a person of ordinaryskill in the art, ILD 190 provides electrical isolation to gateelectrode 150 and the source/drain contacts that will be formed infuture operations (not shown in FIG. 1).

In some embodiments, a combination of a dry and a wet etch processes canused to remove gate electrode 150, which by way of example and notlimitation can be a polysilicon gate electrode. For example, a dry etchprocess can remove a portion of gate electrode 150 so that gateelectrode 150 is recessed with respect to first/second spacers 170, 180,and ILD 190. An exemplary wet etch process, according to someembodiments, can then selectively remove any remaining material of gateelectrode 150. If the wet etch process has poor selectivity for gateelectrode 150 then, during the polysilicon removal process, firstspacers 170 and gate dielectric 160 will be partially removed. As aresult, the wet etch chemistry can reach substrate 110. Further,assuming substrate 110 is made of silicon, the wet etch chemistry canbegin to etch through the silicon substrate 110, resulting in siliconloss. As explained earlier, silicon loss from substrate 110 is areliability concern and can result in wafer yield loss.

FIG. 2 shows an exemplary transistor structure 200 after the removal ofthe polysilicon gate electrode with a dry etch process and a subsequentwet etch process that exhibits poor etch selectivity between gateelectrode 150, first spacers 170, and gate dielectric 160. In thisexemplary case, first spacers 170 and gate dielectric 160 are etchedsubstantially at “weak-point” locations where gate dielectric 160 andfirst spacer 170 could be thinner such as, for example, the bottomcorners of gate structure 140. These weak-points can occur duringdeposition and can be attributed to the deposition technique, thegeometrical characteristics of the structure (e.g., aspect ratio andopening profile), the thickness of each layer, and other parameters. Asa result, portions of substrate 110 can be exposed to the wet etchchemistry, which can etch the exposed surfaces of substrate 110.Consequently, cavities 210 are formed in substrate 110 at the locationswhere the substrate and the wet etch chemistry come into contact. Sincesubstrate 110 can be a single crystal material (e.g., silicon), the sizeand the shape of cavities 210 may vary depending on, for example, theetching time, crystallographic orientation of the substrate, dopinglevel of the substrate, and mechanical stress. As would be understood bya person of ordinary skill in the art, cavities 210 can pose a seriousreliability concern and lead to poor wafer yield. More importantly,cavities 210 can be random across the wafer and affect many areas of thechip.

An exemplary wet etch chemistry is disclosed herein to address the aboveissues. In some embodiments, the exemplary wet etch chemistry has thefollowing attributes: (i) high selectivity to Si over Si-based oxides,nitrides and carbides; (ii) good wettability to reduce surface tensionand allow the chemical solution to reach the targeted surfaces; and(iii) a buffer system to ensure the solution's strength (e.g., etchingrate stability) is consistent over time.

With regard to selectivity, in some embodiments, the solution'sselectivity can be tailored in two ways: (i) enhancing the polysiliconetch rate, and (ii) impeding the etch rate of other Si-based materials(e.g., Si-based oxides, nitrides, and carbides). In some embodiments,the polysilicon etch can be enhanced with the introduction of inorganicfluoride-based chemicals or inorganic alkalis such as hydrofluoric acid(HF) and ammonium hydroxide (NH₄OH). According to some embodiments, theaddition of an organic alkali that features a steric hindrance aminestructure can assist with the polysilicon etch and inhibit the etch ofSi-based oxides, nitrides, and carbides. Therefore, the organic alkalithat features a steric hindrance amine structure can have a dualfunction.

As would be understood by a person of ordinary skill in the art, sterichindrance is the prevention, or retardation, of inter- orintra-molecular interactions as a result of the spatial structure of amolecule. In other words, a steric hindrance amine structure can createa “layer” around the Si-based oxides, nitrides, and carbides to protectthem from the etching components of the wet chemistry. The formation ofthis “protection layer” is attributed to the large size of the sterichindrance amine structure which prohibits the chemical solution fromreaching and reacting with the Si-based oxides, nitrides, and carbides.In some embodiments, chemicals that possess a steric hindrance aminestructure and could be used in an exemplary wet chemistry includetetramethyl ammonium hydroxide (TMAH), tetrabutylammonium hydroxide(TBAH), benzyltrimethylammonium hydroxide, and monoethanolamine (MEA).As would be understood by a person of ordinary skill in the art, theetching solution may contain more than one of the aforementioned sterichindrance amines. The steric hindrance amines can inhibit or retard theSi-based oxide, nitride, and carbide etch but continue to provide goodetching rates for polysilicon or a-Si. Therefore, these organic alkaliscan complement the inorganic etching chemicals and provide protection tothe etching-sensitive layers of the structure.

In some embodiments, in addition to the organic alkalis with a sterichindrance structure, a polar solvent can also provide wet etchprotection for gate dielectric 160, first spacers 170, second spacers180 and ILD 190, which are Si-based oxide, nitride and carbide layers.Polar solvents can be organic or inorganic chemicals with atoms havingdifferent electronegativities. In some embodiments, the polar solventcan be organic solvents with high polarity, namely greater than 4. Byway of example and not limitation, high polar organic solvents that canbe added to the etching solution include sulfone derivatives, carbonateester derivatives, ether derivatives, alcohol derivatives, and furanderivatives. In some embodiments, to protect silicon oxides and siliconnitrides, polar solvents that can be used include dimethyl sulfoxide,sulfolane, ethylene carbonate, tetrahydrofuran, butyl diglycol, andethylene glycol (EG). As would be understood by a person of ordinaryskill in the art, the aforementioned polar solvents are not intended tobe limiting. The concentration ratio for the polar solvent in theetching solution can range from 1% to 40%, according to someembodiments.

With regard to wettability, in some embodiments, a surfactant can beused to improve the wettability of the solution on the surfaces ofstructure 100. Surfactants are compounds that lower the surface tension(or interfacial tension) between two liquids or between a liquid and asolid. Among other things, surfactants can be used as wetting agents.For example, fluorine-containing surfactants can be used according tosome embodiments. In some embodiments, the use of a surfactant can beoptional since some components of the wet etch chemistry—e.g., one ofthe organic solvents—may improve the solution's wettability. By way ofexample and not limitation, EG (which is a polar solvent that can beadded to the organic solvent mixture to protect Si-based oxide, nitride,and carbide layers) can also improve the solution's wettability. Inaddition, EG does not participate in the reaction and forms hydrogenbonds with water in the solution. EG can therefore mitigate water lossduring the etching process.

With regard to the buffer system, as the etching process progresses, theetching solution tends to lose its “strength” (etching ability) due tothe consumption of its chemicals. In addition, the formation ofbyproducts, which are diluted into the etching solution, can alsocompromise its effectiveness over time. In some embodiments, a buffersystem can mitigate these issues. As would be understood by a person ofordinary skill in the art, a buffer system is an aqueous solution thatprovides pH stability during the etching process regardless whether abase or an acid is added. According to some embodiments, the buffersystem can provide hydroxide (OH⁻) to the solution to sustain thechemical reactions and to retain the polysilicon etching selectivity. Inaddition, the buffer system can ensure that the polar solvents and theorganic alkali solvents with steric hindrance amine structures continueto protect the Si-based oxide, nitride, and carbide layers. According tosome embodiments, solvents that are already present in the solution canalso act as a buffer system. By way of example and not limitation, TMAHand MEA are organic solvents that can be used as the solution's buffersystem.

The solution's strength can also be maintained with a process known as“bulk chemical spiking.” Spiking is a method during which smallquantities of certain chemicals are replenished during the etch process.Chemicals that can be replenished are water, bulk chemicals like HF, andsimple alkalis. In some embodiments, few milliliters of chemicals areadded to the solution every 2 to 200 s. The spiking process can beautomated and can be built into the wet etch recipe used by the wet etchequipment. Spiking can extend the lifetime of the etching solution andensure consistent etching rate between wafers or between batches ofwafers (lots). Extending the lifetime of the etching solution cansignificantly reduce the chip manufacturing cost. As would be understoodby a person of ordinary skill in the art, a combination of a buffersystem and spiking is possible for an exemplary wet etch processaccording to some embodiments.

Based on the above, in some embodiments, an exemplary wet etch chemistrycan include at least the following components: a polar solvent, analkaline solvent, a surfactant, and water. As would be understood by aperson of ordinary skill in the art, the solution described above is a“semi-aqueous” system. In other words, the solution includes at leasttwo organic solvents (e.g., a polar solvent and an alkaline solvent)dissolved in water.

In some embodiments, an exemplary polysilicon wet etch solution caninclude at least 40% MEA, at least 5% EG, no more than 1% TMAH, at least10% water, and 0% surfactants. According to some embodiments, anexemplary wet etch solution with the aforementioned solvents and asolution temperature of 60° C. can have a polysilicon etch rate greaterthan 700 Å/min and a-Si etch rate greater than 200 Å/min. Meanwhile, theSiO₂ etch rate can be less than 0.03 Å/min, and the Si_(x)N_(y) orSiO_(x)C_(y) etch rate can be less than 0.110 Å/min. The aforementionedetch rates translate to the following etch selectivity ratios: forpolysilicon to SiO₂, 26000:1 or greater; for polysilicon to Si_(x)N_(y)(or SiO_(x)C_(y)) 6000:1 or greater; for a-Si to SiO₂, 9000:1 orgreater; and for a-Si to Si_(x)N_(y) (or SiO_(x)C_(y)), 2000:1 orgreater. As would be understood by a person of ordinary skill in theart, the aforementioned combination of chemicals, their concentrationpercentages in the solution, and the resulting etch selectivity ratiosfor polysilicon and a-Si are not intended to be limiting and areprovided only as an example. As a result, other chemical combinations,alternative concentrations and resulting etch selectivity ratios arepossible.

According to some embodiments, the following reactions may occur duringthe etching process:(CH₂H)₄N⁺OH⁻+OH⁻→(CH₃H)₄N⁺+2OH⁻  (1)SiO_(2(s))+OH⁻→SiO₃H⁻  (2a)SiO₃H⁻+OH⁻↔SiO₃ ²⁻+H₂O  (2b)NH₂(CH₂)₂OH+H₂O→(NH₃)⁺OH⁻(CH₂)₂OH  (3a)(NH₃)⁺OH⁻(CH₂)₂OH→(NH₂)⁺(CH₂)₂OH+OH⁻  (3b)Reaction (1) describes the TMAH dissociation to OH⁻. Reactions (2a) and(2b) describe the conversion of solid (denoted as “_((s))” next to SiO₂in reaction (2a)) SiO₂ by OH⁻ to water-soluble silicate ions and water(reaction 2b). Finally, reactions (3a) and (3b) describe the MEAdilution in water after dissociation, supplemented with OH⁻ from TMAHthat maintain the stability of the etching solution. The buffer system(MEA and TMAH) provide the OH⁻ groups for the TMAH dissociation inreaction (1). As would be understood by a person of ordinary skill inthe art, reactions (1), (2a), 2(b), 3(a), 3(b) may not be executed inthe order presented above and can be executed in a different order.

According to some embodiments, the chemicals of the etching solution aremixed inside the wet clean tool before the solution can be dispensed onthe wafer. According to some embodiments, the wet etch chemistry isdesigned to work with single-wafer tools where the etching conditionscan be tightly controlled. Examples of the etching conditions includethe dispense angle of the solution with respect to the surface of thewafer, the etch time, the wafer temperature, and the solutiontemperature.

FIG. 3 shows a flow chart of an exemplary replacement gate process 300that utilizes an exemplary wet etch chemistry for polysilicon gateelectrode removal, according to some embodiments. Other fabricationoperations may be performed between the operations of method 300 and areomitted merely for clarity. As would be understood by a person ofordinary skill in the art, the exemplary replacement gate process 300 isnot limited to the operations described below.

Exemplary replacement gate process 300 starts with operation 305 where asacrificial gate stack is formed on a substrate. The sacrificial gatestructure can include a sacrificial gate electrode 150 and a sacrificialgate dielectric 160 as shown in FIG. 4. By way of example and notlimitation, the sacrificial gate electrode 150 can be made ofpolysilicon, and the sacrificial gate dielectric 160 can be made ofSiO₂. The gate stack can be formed, for example, with a blanket SiO₂deposition followed by blanket polysilicon deposition. The resultingstack is then patterned using photolithography and etch operations.Semiconductor substrate 110 can be a bulk wafer or the top layer of anSOI wafer. If exemplary structure 100 is a finFET, then semiconductorsubstrate 110 can be a semiconductor fin that is perpendicular to thewafer's top surface. By way of example and not limitation, semiconductorsubstrate 110 can be made of silicon, another elementary semiconductor,or a compound semiconductor.

In operation 310, a pair of first spacers 170 can be formed on thesidewalls of the gate stack as shown in FIG. 5. By way of example andnot limitation, the spacer formation can include a blanket deposition offirst spacer material that is uniformly deposited over all surfacese.g., horizontal and vertical surfaces. An etch-back process can removethe blanket deposition on the horizontal surfaces such as the topsurface of gate electrode 150 and substrate 110. The etch-back processcan be anisotropic (e.g., single-direction) and can be automaticallyterminated when the gate electrode material is exposed. Consequently, atthe end of the etch-back process, each sidewall surface of gateelectrode 150 is covered with a layer of first spacer material. As wouldbe understood by a person of ordinary skill in the art, first spacer 170can be a dielectric material such as, for example, SiO₂, SiON, SiCN,SiO_(x)C_(y) or Si_(x)N_(y). In some embodiments, the thickness of firstspacers 170 can range from about 2 to about 5 nm.

In operation 315, the first spacers 170 and gate electrode 150 can beused as an implant mask to form source/drain extensions (or LID)implants. Such implants can be p-type or n-type. By way of example andnot imitation, boron can be used as a p-type implant and arsenic,phosphorous, or antimony can be used as an n-type implant. Thesource/drain extension regions 120 as shown in FIG. 6 are placed at aclose proximity to the edge of the channel region 600 (underneath thegate stack), as defined by the thickness of first spacers 170, toprovide a gradual dopant concentration to the source/drain regions whichwill be formed in operation 325. The source/drain extensions createlateral and vertical doping profiles in the interface region of thechannel edge. As would be understood by a person of ordinary skill inthe art, the source/drain extensions mitigate high electric fields thatmay be present between the source/drain regions and channel region 600during transistor operation.

Exemplary process 300 continues with operation 320 where second spacers180 as shown in FIG. 7 can be formed. Second spacers 180 can be formedin a similar manner as first spacers 170—e.g., with a blanket depositionof the second spacer material and an etch-back process. In someembodiments, second spacers 180 can be made of a dielectric materialsuch as, for example, SiON, Si_(x)N_(y), or SiCN. As would be understoodby a person of ordinary skill in the art, second spacers 180 can be astack of one or more layers made of the same or different materials.

In operation 325, the gate stack, the first spacers 170 and secondspacers 180 can be used as a mask for the main implants to form thesource/drain regions 130 as shown in FIG. 8. Source/drain regions 130are heavily doped regions that have higher dopant concentrations and arelarger in size than source/drain extensions 120. Regions 130 and 120 arerequired to have the same type and kind of dopants. After thesource/drain region 130 formation, an ILD layer can be formed toelectrically isolate gate stack 140. By way of example and notlimitation, the ILD formation can begin with a blanket deposition of ILDmaterial over substrate 110 and gate stack 140. A chemical mechanicalplanarization (CMP) process can be used to remove excess ILD materialand to planarize it so that the top surface of the ILD material and thetop surface of gate stack 140 are aligned. FIG. 1 shows the resultingstructure where ILD layer 190 abuts the sidewall surfaces of gate stack140. In some embodiments, ILD 190 can be SiO₂, SiOC, SiON, SiOCN, SiC,or SiCN.

In operation 330, the sacrificial polysilicon gate electrode 150 can beremoved. In some embodiments, sacrificial polysilicon gate electrode 150can be removed in a two-step process. For example, in a first step, aportion of the sacrificial polysilicon gate electrode 150 can be removedwith a dry etch process. And in a second step, sacrificial polysilicongate electrode 150 can be removed with an exemplary wet etch process. Byway of example and not limitation, the dry etch process can recess thesacrificial polysilicon gate electrode 150 with respect to first spacers170, second spacers 180, and ILD 190 as shown in FIG. 9. By way ofexample and not limitation, the exemplary wet etch process canselectively remove polysilicon without substantially removing firstspacer 170 and gate dielectric 160.

According to some embodiments, the exemplary wet etch chemistry caninclude at least a polar solvent, an alkaline solvent, an optionalsurfactant, and water. In some embodiment, the wet etch chemistry hasthe following attributes: (i) high selectivity to Si over Si-basedoxides, nitrides, and carbides; (ii) good wettability to reduce surfacetension and allow the chemical solution to reach the targeted surfaces;and (iii) a buffer system to ensure that the solution's strength (e.g.,etching rate stability) is consistent over time.

In some embodiments, selectivity can be tailored in two ways: (i) byenhancing the polysilicon etch rate; and (ii) by impeding the etch rateof other Si-based materials (e.g., Si-based oxides, nitrides, andcarbides). In some embodiments, the polysilicon etch can be enhancedwith the introduction of inorganic fluoride-based chemicals or inorganicalkalis such as HF and NH₄OH. According to some embodiments, theaddition of an organic alkali that features a steric hindrance aminestructure can assist with the polysilicon etch and inhibit the etch ofSi-based oxides, nitrides, and carbides. Therefore, these organicalkalis can complement the inorganic etching chemicals and provideprotection to the etching-sensitive layers of the structure. By way ofexample and not limitation, chemicals that possess a steric hindranceamine structure and can be used in the exemplary wet chemistry includeTMAH, TBAH, benzyltrimethylammonium hydroxide, or MEA.

In addition to the organic alkalis with a steric hindrance aminestructure, a polar solvent can also provide wet etch protection for gatedielectric 160, first spacers 170, second spacers 180 and ILD 190 (e.g.,Si-based oxide, nitride, and carbide layers). In some embodiments, thepolar solvent selection can be organic solvents with high polarity,namely greater than 4. By way of example and not limitation, high polarorganic solvents that can be added to the etching solution includesulfone derivatives, carbonate ester derivatives, ether derivatives,alcohol derivatives, and furan derivatives. To protect SiO₂ andSi_(x)N_(y), polar solvents that can be used include dimethyl sulfoxide,sulfolane, ethylene carbonate, tetrahydrofuran, butyl diglycol, and EG.As would be understood by a person of ordinary skill in the art, theaforementioned polar solvents are not intended to be limiting and theconcentration ratio for the polar solvent in the solution can range from1% to 40%.

Wettability of the etching solution on the surfaces of structure 100 ofFIG. 1 can be improved with the use of a surfactant. Fluorine-containingsurfactants can be used according to some embodiments. In someembodiments, the use of a surfactant is optional since some componentsof the wet etch chemistry—e.g., one of the organic solvents—may improvethe solution's wettability. By way of example and not limitation, EG(which is a polar solvent that can be added to the organic solventmixture to protect Si-based oxide, nitride, and carbide layers) can alsoimprove the solution's wettability. In addition, EG does not participatein the reaction and forms hydrogen bonds with water in the solution. Itcan therefore mitigate water loss during the etching process.

A buffer system can ensure that the etching solution retains itsstrength or etching ability. For example, byproducts that are dilutedinto the solution, can compromise the solution's etching ability overtime. As would be understood by a person of ordinary skill in the art, abuffer system is a semi-aqueous solution that provides pH stabilityduring the etching process regardless whether a base or an acid isadded. According to some embodiments, the buffer system can provide OH⁻to the solution to sustain the chemical reactions and retain thepolysilicon etching selectivity. The buffer system can also ensure thatthe polar solvents and the organic alkali solvents with steric hindranceamine structures continue to protect the Si-based oxide, nitride, andcarbide layers. According to some embodiments, solvents that are alreadypresent in the solution can also act as a buffer system. By way ofexample and not limitation, TMAH and MEA are organic solvents that canfunction as the solution's buffer system.

The solution's strength can also be maintained by bulk chemical spiking,as described above. Chemicals that can be replenished are water, bulkchemicals like HF, and simple alkalis. In some embodiments, fewmilliliters of chemicals are added to the solution every 2 to 200 s.Spiking can extend the lifetime of the etching solution and ensureconsistent etching rate between wafers or between lots. Extending thelifetime of the etching solution can reduce the chip manufacturing cost.A combination of a buffer system and spiking can be used in theexemplary wet etch solution, according to some embodiments.

In some embodiments, the exemplary polysilicon wet etch solution caninclude at least 40% MEA, at least 5% EG, no more than 1% TMAH at least10% water, and 0% surfactants. According to some embodiments, anexemplary wet etch solution with the aforementioned solvents and asolution temperature of 60° C. can have a polysilicon to SiO₂ etchselectivity ratio greater than 26000:1, a polysilicon to Si_(x)N_(y) (orSiO_(x)C_(y)) etch selectively ratio greater than 6000:1; an a-Si toSiO₂ etch selectivity ratio greater than 9000:1, and a-Si to Si_(x)N_(y)(or SiO_(x)C_(y)) etch selectivity ratio greater than 2000:1. As wouldbe understood by a person of ordinary skill in the art, theaforementioned combination of chemicals, their concentration percentagesin the solution, and the resulting etch selectivity ratios are notintended to be limiting and are provided only as an example.Consequently, other solvent combinations, alternative concentrations andresulting etch selectivity ratios are possible for the wet etchsolution.

In operation 335 of exemplary process 300, the remaining sacrificialgate dielectric layer 160 can be removed with a wet etch and can bereplaced with a high-k dielectric such as, for example, HfO₂,Hf-silicate, or a stack of dielectric materials. The stack of dielectricmaterials can be, for example, SiO₂/HfO₂, silicon oxynitride/HfO₂ orSiO₂/Hf-silicate, silicon oxynitride/Hf-silicate, or any othercombination of suitable high-k dielectrics. The metal gate electrode canbe different depending on the type of transistor (p-type or n-type) andthe work function requirement for each. Exemplary p-type work functionmetals that may be included in the metal gate structure include titaniumnitride (TiN), tantalum nitride (TaN), ruthenium (Ru), molybdenum (Mo),aluminum (Al), tungsten nitride (WN), zirconium silicide (ZrSi₂),molybdenum silicide (MoSi₂), tantalum silicide (TaSi₂), nickel silicide(NiSi₂), tungsten nitride (WN), other suitable p-type work functionmaterials, or combinations thereof. Exemplary n-type work functionmetals that may be included in the metal gate structure include titanium(Ti), silver (Ag), tantalum-aluminum alloy (TaAl), tantalum-aluminumcarbide (MAW), tantalum-aluminum nitride (TiAlN), tantalum carbide(TaC), tantalum carbon nitride (TaCN), tantalum silicon nitride (TaSiN),manganese (Mn), zirconium (Zr), other suitable n-type work functionmetals/alloys, or combinations thereof. By way of example and notlimitation, the gate electrode dielectric and metal gate electrode canbe deposited with atomic layer deposition (ALD), chemical vapordeposition (CVD), or any other suitable deposition process.

The present disclosure is directed to an exemplary wet etch chemistrythat exhibits selectivity ratios greater than 2000:1 for polysilicon anda-Si over SiO₂, Si_(x)N_(y), and SiO_(x)C_(y). In some embodiments, thiscan be accomplished with the use of a semi-aqueous solution with aco-solvent system. The co-solvent system includes of at least twoorganic solvents, an alkaline solvent, and a polar solvent. An advantageof this approach is that the co-solvent system is configured so that thealkaline and polar solvent combination can fulfill different aspects ofthe solution simultaneously. For example, protection for SiO₂,Si_(x)N_(y), or SiO_(x)C_(y) can be achieved with the use of an organicalkaline solvent that features a steric hindrance amine structure and apolar solvent with polarity greater than 4. At the same time, a polarsolvent such as EG can improve the wettability of the etching solution,and the combination of TMAH and MEA (organic alkaline solvent thatfeatures a steric hindrance amine structure) can operate as a buffersystem. Another advantage of the exemplary wet etch chemistry is theability to use spiking which can extend the lifetime of the solution.

In some embodiments, a wet etch chemistry includes: one or more alkalinesolvents with a steric hindrance amine structure; a buffer system thatincludes tetramethylammonium hydroxide (TMAH) and monoethanolamine(MEA); one or more polar solvents; and water.

In some embodiments, a semiconductor fabrication method includes a gatestack structure with a polysilicon gate electrode is formed over a gatedielectric with a dielectric layer abutting the side surfaces of thegate stack structure. The polysilicon gate electrode is selectivelyremoved with a wet etch chemistry, where the wet etch chemistry includesone or more alkaline solvents—with at least one of the alkaline solventshaving a steric hindrance amine structure—and one or more polar solventshaving a polarity greater than 4.

In some embodiments, a wet etch chemistry, that can selectively etchpolysilicon or amorphous silicon in a gate replacement process,includes: an inorganic fluoride-based chemical or an inorganic alkali;one or more organic alkaline solvents with a steric hindrance aminestructure; one or more polar solvents; and water.

The foregoing outlines features of embodiments so that those skilled inthe art may better understand the aspects of the present disclosure.Those skilled in the art should appreciate that they may readily use thepresent disclosure as a basis for designing or modifying other processesand structures for carrying out the same purposes and/or achieving thesame advantages of the embodiments introduced herein. Those skilled inthe art should also realize that such equivalent constructions do notdepart from the spirit and scope of the present disclosure, and thatthey may make various changes, substitutions, and alterations hereinwithout departing from the spirit and scope of the present disclosure.

What is claimed is:
 1. A wet etch chemistry comprising: one or morealkaline solvents, wherein at least one of the alkaline solventscomprises a steric hindrance amine structure; a buffer system comprisingtetramethylammonium hydroxide (TMAH) and monoethanolamine (MEA); one ormore polar solvents; and water.
 2. The wet etch chemistry of claim 1,wherein the one or more polar solvents have a polarity greater than 4.3. The wet etch chemistry of claim 1, further comprising: an inorganicfluoride-based chemical or an inorganic alkali.
 4. The wet etchchemistry of claim 3, wherein the inorganic fluoride-based chemical andthe inorganic alkali comprise hydrofluoric acid (HF) and ammoniumhydroxide (NH₄OH), respectively.
 5. The wet etch chemistry of claim 1,wherein the wet etch chemistry comprises a semi-aqueous systemcomprising monoethanolamine (MEA), ethylene glycol (EG),tetramethylammonium hydroxide (TMAH), water, and a fluorine-containingsurfactant, and wherein a polysilicon to silicon oxide selectivity ratiocan be greater than 26000:1 and a polysilicon to silicon nitride(Si_(x)N_(y)) selectivity ratio or a polysilicon to silicon oxy-carbide(SiO_(x)C_(y)) selectivity ratio can be greater than 6000:1.
 6. The wetetch chemistry of claim 1, wherein the at least one of the alkalinesolvents having the steric hindrance amine structure comprisestetramethylammonium hydroxide (TMAH), tetrabutylammonium hydroxide(TBAH), benzyltrimethylammonium hydroxide, or monoethanolamine (MEA). 7.The wet etch chemistry of claim 1, wherein the one or more polarsolvents comprise sulfone derivatives, carbonate ester derivatives,ether derivatives, alcohol derivatives, furan derivatives, dimethylsulfoxide, sulfolane, ethylene carbonate, tetrahydrofuran, butyldiglycol, and ethylene glycol (EG).
 8. A wet etch chemistry toselectively etch polysilicon or amorphous silicon in a gate replacementprocess, the wet etch chemistry comprising: an inorganic fluoride-basedchemical or an inorganic alkali; one or more organic alkaline solvents,with at least one of the alkaline solvents having a steric hindranceamine structure; one or more polar solvents; and water.
 9. The wet etchchemistry of claim 8, wherein the at least one alkaline solvents havingthe steric hindrance amine structure comprises tetramethylammoniumhydroxide (TMAH), tetrabutylammonium hydroxide (TBAH),benzyltrimethylammonium hydroxide, or monoethanolamine (MEA).
 10. Thewet etch chemistry of claim 8, wherein the one or more polar solventshave a polarity greater than 4 and comprise sulfone derivatives,carbonate ester derivatives, ether derivatives, alcohol derivatives,furan derivatives, dimethyl sulfoxide, sulfolane, ethylene carbonate,tetrahydrofuran, butyl diglycol, and ethylene glycol (EG).
 11. The wetetch chemistry of claim 8, wherein the inorganic fluoride-based chemicaland the inorganic alkali comprise hydrofluoric acid (HF) and ammoniumhydroxide (NH₄OH), respectively.
 12. The wet etch chemistry of claim 8,further comprising: a buffer system comprising tetramethylammoniumhydroxide (TMAH) and monoethanolamine (MEA).
 13. A wet etch chemistrysolution to selectively etch polysilicon or amorphous silicon in a gatereplacement process, the wet etch chemistry solution comprising:alkaline solvents, polar solvents, or combinations thereof, wherein atleast one of the alkaline solvents comprises a steric hindrance aminestructure and the polar solvents have a polarity greater than 4; aninorganic fluoride based chemical or an inorganic alkali; a buffersystem comprising tetramethylammonium hydroxide (TMAH) andmonoethanolamine (MEA); and a fluorine-containing surfactant.
 14. Thewet etch chemistry solution of claim 13, wherein a concentration of thepolar solvents ranges from 1% to 40%.
 15. The wet etch chemistrysolution of claim 13, wherein the polar solvents comprise sulfonederivatives, carbonate ester derivatives, ether derivatives, alcoholderivatives, furan derivatives, dimethyl sulfoxide, sulfolane, ethylenecarbonate, tetrahydrofuran, butyl diglycol, and ethylene glycol (EG).16. The wet etch chemistry solution of claim 13, wherein the at leastone of the alkaline solvents comprises tetrabutylammonium hydroxide(TBAH).
 17. The wet etch chemistry solution of claim 13, wherein the MEAis at least 40% of the wet etch chemistry, an ethylene glycol (EG) is atleast 5% of the wet chemistry, and the TMAH is less than 1% of the wetetch chemistry.
 18. The wet etch chemistry solution of claim 13, furthercomprising at least 10% water.
 19. The wet etch chemistry solution ofclaim 13, wherein the at least one of the alkaline solvents comprisestetrabutylammonium hydroxide (TBAH).
 20. The wet etch chemistry solutionof claim 13, wherein the inorganic fluoride-based chemical and theinorganic alkali comprise hydrofluoric acid (HF) and ammonium hydroxide(NH₄OH), respectively.